Andris, Erik

Bill, Eckhard

Costas, Miquel

Gamba, Ilaria

Lazaro, Laura

Lloret-Fillol, Julio

Martin-Diaconescu, Vlad

Neese, Frank

Roithova, Jana

Sabenya, Gerard

Weyhermüller, Thomas

English

Iron complex [FeIII(N3)(MePy2tacn)](PF6)2 (1), containing a neutral triazacyclononane-based pentadentate ligand, and a terminally bound azide ligand has been prepared and spectroscopically and structurally characterized. Structural details, magnetic susceptibility data, and Mössbauer spectra demonstrate that 1 has a low-spin (S = 1/2) ferric center. X-ray diffraction analysis of 1 reveals remarkably short Fe–N (1.859 Å) and long FeN–N2 (1.246 Å) distances, while the FT-IR spectra show an unusually low N–N stretching frequency (2019 cm–1), suggesting that the FeN–N2 bond is particularly weak. Photolysis of 1 at 470 or 530 nm caused N2 elimination and generation of a nitrido species that on the basis of Mössbauer, magnetic susceptibility, EPR, and X-ray absorption in conjunction with density functional theory computational analyses is formulated as [FeV(N)(MePy2tacn)]2+ (2). Results indicate that 2 is a low-spin (S = 1/2) iron(V) species, which exhibits a short Fe–N distance (1.64 Å), as deduced from extended X-ray absorption fine structure analysis. Compound 2 is only stable at cryogenic (liquid N2) temperatures, and frozen solutions as well as solid samples decompose rapidly upon warming, producing N2. However, the high-valent compound could be generated in the gas phase, and its reactivity against olefins, sulfides, and substrates with weak C–H bonds studied. Compound 2 proved to be a powerful two-electron oxidant that can add the nitrido ligand to olefin and sulfide sites as well as oxidize cyclohexadiene substrates to benzene in a formal H2-transfer process. In summary, compound 2 constitutes the first case of an octahedral FeV(N) species prepared within a neutral ligand framework and adds to the few examples of FeV species that could be spectroscopically and chemically characterized

Sabenya, G.

Lázaro, L.

Gamba, I.

Martin-Diaconescu, V.

Andris, E.

Weyhermüller, T.

Neese, F.

Roithova, J.

Bill, E.

Lloret-Fillol, J.

Costas, M.

MPG.PuRe

Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

See the paper.Funded under Horizon2020.
This document is the unedited Author´s version of a Submitted Work that was subsequently accepted for publication in the Journal of the American Chemical Society, copyright © American Chemical Society after peer review

ZENODO

RECERCAT

Generation, spectroscopic and chemical characterization of an   octahedral iron (V) – nitrido species with a neutral ligand platform

Roithová, Jana

Generation, spectroscopic and chemical characterization of an octahedral iron (V) – nitrido species with a neutral ligand platform

Iron
complex [FeIII(N3)­(MePy2tacn)]­(PF6)2 (1), containing a neutral triazacyclononane-based
pentadentate ligand, and a terminally bound azide ligand has been
prepared and spectroscopically and structurally characterized. Structural
details, magnetic susceptibility data, and Mössbauer spectra
demonstrate that 1 has a low-spin (S = 1/2) ferric center. X-ray diffraction analysis of 1 reveals remarkably short Fe–N (1.859 Å) and long FeN–N2 (1.246 Å) distances, while the FT-IR spectra show an
unusually low N–N stretching frequency (2019 cm–1), suggesting that the FeN–N2 bond is particularly
weak. Photolysis of 1 at 470 or 530 nm caused N2 elimination and generation of a nitrido species that on the basis
of Mössbauer, magnetic susceptibility, EPR, and X-ray absorption
in conjunction with density functional theory computational analyses
is formulated as [FeV(N)­(MePy2tacn)]2+ (2). Results indicate that 2 is a low-spin
(S = 1/2) iron­(V) species, which exhibits a short
Fe–N distance (1.64 Å), as deduced from extended X-ray
absorption fine structure analysis. Compound 2 is only
stable at cryogenic (liquid N2) temperatures, and frozen
solutions as well as solid samples decompose rapidly upon warming,
producing N2. However, the high-valent compound could be
generated in the gas phase, and its reactivity against olefins, sulfides,
and substrates with weak C–H bonds studied. Compound 2 proved to be a powerful two-electron oxidant that can add
the nitrido ligand to olefin and sulfide sites as well as oxidize
cyclohexadiene substrates to benzene in a formal H2-transfer
process. In summary, compound 2 constitutes the first
case of an octahedral FeV(N) species prepared within a
neutral ligand framework and adds to the few examples of FeV species that could be spectroscopically and chemically characterized

Gerard Sabenya (1312986)

Laura Lázaro (4216273)

Ilaria Gamba (3132540)

Vlad Martin-Diaconescu (1352397)

Erik Andris (2568652)

Thomas Weyhermüller (1456042)

Frank Neese (736441)

Jana Roithova (4216276)

Eckhard Bill (1309914)

Julio Lloret-Fillol (1312989)

Miquel Costas (795606)

FigShare

Generation,
Spectroscopic, and Chemical Characterization
of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

https://figshare.com/articles/Generation_Spectroscopic_and_Chemical_Characterization_of_an_Octahedral_Iron_V_-Nitrido_Species_with_a_Neutral_Ligand_Platform/5161396

Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

Abstract

Similar works

Full text

Available Versions

MPG.PuRe

ZENODO

RECERCAT

ZENODO

FigShare

FigShare